Alkylation of aromatic hydrocarbons



United States Patent Ofice ALKYLATION OF AROMATIC HYDROCARBONS Abraham Schneider, Philadelphia, Pa., assignor to Sun gil Company, Philadelphia, Pa., a corporation of New ersey Application March 4, 1954, Serial No. 413,988

13 Claims. (Cl. 260--67I)' This invention relates to a catalytic al kylation process, and more particularly to the alkylation of aromatics with isoparafiins under novel catalytic conditions.

Aromatics have heretofore been alkylated with paralhns or naphthenes by what is known as the Fri'edel-Crafts reaction. This reaction, 'as is well known, involves a twostep process wherein the paraflin is chlorinated with chlorine gas, and the alkyl halide thus formed is joined to the aromatic compound by use of a metal halide, such as aluminum chloride. In this process, the chlorine is irreversibly converted to hydrogen chloride and as such According to the invention, when hydrogen fluoride and a tertiary olefin are brought together in the presence of an alkylatable aromatic and a tertiary hydrogen-containing isoparaflin, a catalytic condition is established which is effective to cause such isoparaffin to alkylate the aromatic. Thus, as hereinafter fully illustrated, the present invention provides a one-step process whereby aromatics are alkylated with isoparaflins to produce alkylated aromatics in good yields, and in which process the acid catalyst may be regenerated and recycled. A further advantage is that the present process can be'conducted in the present conventional alkylation contactors, i. e., special apparatus is unnecessary.

The mechanism of the alkylation reaction of the present process is complicated, and is not completely understood. The overall reaction, however, may be expressed by the equation:

wherein AH represents an alkylatable aromatic, RH represents a tertiary hydrogen-containing isoparaifin, isobutylene represents the tertiary olefins which may be employed in the process of the present invention, as hereinafter defined, and AR represents the desired alkylated aromatic product. product, and it has been found characteristic of the present reaction that the tertiary olefin employed is reduced to the corresponding parafiin. It is further characteristic of the alkylated aromatic product of the present process that the alkyl radical attached to the aromatic nucleus contains the same number of carbon atoms as did the isoparafiin. It is also characteristic of the present process that substantially no alkyl fluorides are formed, and practically all of the hydrogen fluoride employed is easily recoverable from the process, and may be recycled thereto.

In practicing the present invention, an emulsion of the It will be noted that isobutane is a aromatic to be alkylated, the tertiary hydrogencontaining 2,712,033 Patented June 28, 1955 isoparaflin and hydrogen fluoride is contacted with a ter tiary olefin. Preferably, a mixture of isoparafiins such as those contained in saturate hydrocarbon fractions is employed. By the term tertiary olefin, as employed herein, is meant a hydrocarbon containing both a carbon to carbon unsaturated double bond and a side chain. By the term saturate, and terms of similar import, as employed herein, is meant a dearomatized hydrocarbon fraction composed substantially of a mixture of branched chain parafiins, including naphthenes, which have at least 5 carbon atoms per molecule, and which contain an average of at least 1 tertiary hydrogen atom per molecule, i. e., a hydrogen atom attached toa carbon atom, which carbon atom in. turn is attached to 3 other carbon atoms, and by the term, isoparafiin, is meant a single such branched chain hydrocarbon, this term being included in the broader term saturate, unless otherwise stated.

The aromatics which may be employed in the process of the present invention are the alkylatable aromatics, i. e.," those m'embers of the aromatic series which have a substitutable position on the aromatic nucleus. Such aromatics include, for example, benzene, toluene, 0-, mand p-xylenes, mixtures of xylenes, ethylbenzene, naph thalene, alpha methyl naphthalene, beta methyl naphthalene, diphenyl, the aromatics contained in hydrocarbon fractions, especially those fractions which have been subjected to cracking, and the like. In general, however, the aromatic to be alkylated should not have more than four substituent groups on the aromatic nucleus. Saturates and isoparaffins which may be employed in the process of the present invention to alkylate the aromatics include, for example, substantially pure isoparaffins con taining from 5 to about 30, and preferably from 5 to 20, carbon atoms per molecule, such as isopentane, Z-methyl heptane, Z-methyl decane, 3-butyl decane, branched chain hexadecanes, heptadecanes, and the like, mixtures thereof, and hydrocarbon fractions containing a substantial proportion of such isoparafiins, alkyl naphthenes such as methyland ethylcyclohexane, and mixtures of such naphthenes and isoparafiins. Saturate petroleum fractions, such as dearor'natiz'ed fractions from catalytic cracking, which contain a substantial proportion of the above and other isooleflns may advantageously be employed. Other hydrocarbons which may be present in such fractions serve as diluents and do not enter the reaction. Such saturate fractions should contain above about 25%, and preferably above 50%, isoparaffins of 5 to 30 carbon atoms having an average of at least 1 tertiary hydrogen atom per molecule. It is preferred to employ isoparaiiins other -than those wherein the carbon atom attached to the tertiary hydrogen atom is in the beta position relative to a quaternary carbon atom, since, as has been found, under the conditions of the present process such isoparaffins do not give, to an appreciable extent, alkylated aromatics wherein the alkyl substituent contains the same number of carbon atoms as the i'soparafiin.

Hydrocarbon fractions, especially those obtained from petroleum, containing both aromatics and saturates may be employed in the'proce'ss of the present invention. By contacting a tertiary olefin with hydrogen fluoride in the presence of such a fraction, a catalytic condition is established whereby the saturates alkylate the aromatics. If desired, a further quantity of aromatics o1" saturates may be added to the fraction to obtain the desired concentration of each. The added aromatics or saturates may be the same as those of the fraction, or different aromatics and saturates may be added and may be so selected that a desired product is obtained.

Tertiary olefins which may be employed in the present process have I olefinic double bond and at least 1 side chain per molecule, and preferably have the tertiary carbon atom attached to the olefinic double bond. The

next preferred tertiary olefins are those which have the olefinic bond in the alpha or beta position relative to the side chain. As illustrative of these compounds may be mentioned isobutylene, which is the preferred tertiary olefin of the present invention, Z-methylbutene-Z; 3- methylbutene- 1; 2.,3-dimethylbutene- 1; 2-methylbut'ene- 3; 4-ethylhexene-1; 6-methylheptene-3; and the' like. A further preferred embodiment of the present invention contemplates the use of cyclic tertiary olefins, such as methylcyclohexene-l, which is a preferred component. methylcyclohexene-3; Z-cyclohexylpropene-l; methylcyclopentene-l; and the like, and it is intended that the term tertiary olefin include such compounds. Olefins which do not meet the above requirements do not cause the desired alkylation reaction to occur to an appreciable extent within the present temperature range. Such olefins might be operable at higher temperatures, but in such case disproportionation and cleavage reactions predominate and preclude recovery of appreciable quantities of the desired alkylated aromatic product.

The quantities of reactants employed in the present process may be substantially varied and good results obtained therewith. From 0.2 to 6 moles of saturate can be employed for each mole of aromatic. i. e., the mole ratio of saturate to aromatic is maintained within the ratio of from 1:5 to 6: l. The quantity of tertiary olefin to employ may advantageously be from 0.1 to 1 mole for each mole of aromatics plus saturates, i. e., a mole ratio of tertiary olefin to aromatics plus isoparaffins of from 1:10 to 1:1, good results being obtained when about,0.4 to 0.6 moles of tertiary olefin for each mole of aromatics plus saturates is employed. It is advantageousto employ an excess of hydrogen fluoride, from about 1 to 8 moles, and preferably from 2 to moles, for each mole of aromatic plus saturate gives good results. Anhydrous hydrogen fluoride gives good results, but hydrogen fluoride admixed with, e. g., hydrocarbon oils or water, wherein the hydrogen fluoride content is above 90%, and preferably above 95%, may be employed.

In practicing the present invention, it is advantageous to maintain the temperature of alkylationfrom above about 50 C. to about 200 C., and preferably between 75 C. and 150 C. Below 50C., the desired alkylation occurs only relatively slowly, and alkylation of the aromatic with the tertiary olefin, instead of the saturate. may occur to an appreciable extent. At temperatures above 200 C. considerable disproportionation of the saturates. and cracking of the alkylated aromatic product, is observed. In general, temperatures of from 75. C. to 150 C. cause the desired alkylation reaction to. progress rapidly, and substantial yields of the desired alkylated aromatic product are obtained. The pressure during alkylation should be sufficient to keep the reactants in the liquid phase. Using the preferred reactants and temperature range of the present invention, pressures of from 100 to 200 p. s. i. are preferred and givegood results, although in some instances, lower or higher pressures may be employed.

The time required for the alkylation varies according to the temperature employed, the reactants. and tertiary olefin employed, their concentrations, and the like, and .is not considered a critical variable, it being obvious that suflicient time should be permitted to obtain the desired product in good yields. In general, an alkylation time of minutes to 2 hours attains thedesired result,

and when preferred reactants, catalyst, and conditions hydrogen fluoride are introduced into the system through lines 1, 2 and 4 respectively. As hereinbefore described,

the saturate employed should contain a substantial pro portion of isoparatfins containing at least l tertiary hydrogen atom per molecule, and preferably should not have the tertiary hydrogen-containing carbon atom in the beta position relative to a quaternary carbon atom. The benzene, saturate, and hydrogen fluoride are passed through heat exchanger 5, which may be either a cooler or a heater, depending on the temperature at which the alkylation is to be performed, and the mixture istthen passed through line 6 into mixer 8, provided with a stirrer. If desired, means (not shown) to heat mixer 8 may be provided. Isobutylene, employed to illustrate the tertiary olefins which may be employed, is introduced in the mixer through line. 9. On contacting the isobutylene with the hydrogen fluoride in the presence of benzene and saturate, a catalytic condition is immediately established whereby the saturate alkylates the benzene.

The reaction mixture leaves mixer 8 through line 10 and ispassed into separator 11, wherein the acid and hydrocarbon phases are separated. The acid phase. usually containing a small amount of dissolved high molecular weight oil, is removed through line 12, and the hydrocarbon phase is passed through line 15 to distillation zone 13. Hydrogen fluoride is easily recovered from the acid phase by distillation (by means not shown) and may be recycled through the process. The distillation zone 13 may advantageously consist of a plurality of such zones from which the various fractions are separated. Isobutane, formedby reduction. of isobutylene is removed through line 14. Benzene may be separated and removed through line 16, and recycled to the process through line 17. The unreacted saturate may be separated through line 18, and recycled through the process through line 19. The desired alkylated aromatic is separated through line 20, and the residue removed through line 21. 1 p

It has been found characteristic of the present process that some of the tertiary olefin employed as a catalyst will be converted to the corresponding paraffin. Thus, if butylene is employed, some isobutane will be formed and may be recovered from the reaction-mixture. A portion thereof, and also a portion of the tertiary olefin, may alkylate the aromatic. Under the conditions described for the present process, especially the preferred conditions, these reactions occur to only a relatively slight extent, and hence do not significantly adversely affect the desired alkylation. In the process illustrated by the flow diagram, some tertiary butylbenzene will be obtained in the reaction mixture. This tertiary butyl benzene may be recycled in the process, since it has been found that the tertiary butyl group, under the conditions of reaction, is cleaved from the benzene, thus providing isobutylene (which serves as the catalyst) and benzene (which is alkylated by the saturates). Likewise, where other tertiary olefins, and/or other aromatics, are employed, any tertiary alkyl aromatic which may be formed may be recycled in the same manner as tertiary butyl benzene.

The following examples illustrate preferred embodiments of the present invention, which is not to be considered as limited theretoz.

Example 1 Into a contactor provided witha stirrer were introduced 200 g. (2.56 moles) benzene, 86 g..( 1.0 mole) 2- rnethylpentane and 145 g. (7.3 moles) anhydrous hydrogen fluoride. Over a period of 15 minutes 73 g."(1.3 moles) isobutylene was added. -The, reaction mixture was then heated to C. for lhour with. stirring, the pressure being 200 p. s. i. The reaction mixture was cooled and the organic layer washed with 'water. Isobutane' was separated by distillatioma total of 41.4 g. (0.71 mole) being obtained. The remaining hydrocarbon mixture was dried and the components thereof separated by distillation. There were obtained 40.0 g. of Z-methylpentane, 134.5 g. benzene, and'53.5 vg of amixture of hexylbenzene iso- There were also obtained 27.5 g. of t-butyl benzene (boiling point=l69 0.), 6.5 g. di-t-butylbenzene (boiling point=237 C.), and 13 g. residue. The hexylbenzene isomers were collected in the temperature range of from 178 C. to 215 C. at atmospheric pressure, and had a refractive index n =1.4952.

The yield of hexylbenzenes, based on benzene consumed and considering the t-butylbenzene and di-t-butylbenzene as stock for recycling, was 61%. The weight percent of hexylbenzene isomers in the (Z-methylpentane free) alkylate was 24.1, and of tertiary butyl benzene was 12.7. This shows the large yield of the product of alkylation of the aromatic with the isoparafiiu as compared to the yield of the product of alkylation of the aromatic by the tertiary-olefin,

' Examplei Benzene was alkylated with the hydrocarbons of a petroleum saturate fraction having an average molecular weight of 250 and an average of 2.2 naphthene rings per molecule as follows: 150 g. (1.92 moles) of benzene, 140 g. (0.560 mole) of saturates, and 193 g. of hydrogen fluoride were admixed and 62 g. 1.11 moles) of isobutylene added to the stirred admixture at room temperature. The temperature was increased to 95 C. and the "reaction mixture stirred at this temperature for 45 minutes. The layers were then allowed-to stratify and were separated by decanting. There were recovered two layers, 201 g. of a hydrogen fluoride layer and 333 g. oforganic layer.' The recovered organic layer was washed, dried, and the components thereof separated by distillation. There were recovered the-following:

Alkylated benzene product 45.3 g., 0.145 mole. Isobutane -3 16.1 g.,;0.278 mole. Benzene 82.8 g., 1.06 moles. Tertiary butyl benzene 45.9 g., 0.342 mole. Ditertiary butyl benzene 11.7 g., 0.062 mole. Saturates 103.3 g., 0.413 mole.

The alkyl group of the alkylated benzene product had the same number of carbon atoms'as the saturates from the petroleum fraction. The alkylated benzene product had a molecular weight of 312 (determined by viscosity correlations) as compared to a theoretical molecular weight of 328. Further analysis of the product showed that there were an average of 2.6 naphthene rings per molecule and an average of 1.1'aromatic rings per molecule. These data show that naphthene rings of saturate hydrocarbons are not cleaved inthe alkylation process.

Example 3 Benzene was alkylated, using the procedure of Example 1, with saturate fractions from three different crudes: dearomatized straight run naphtha having a molecular weight of 156, and n =1.4279 (run A); dearomatized East Texas straight run gasoline, boiling range 100-490 (2., having an average of carbon atoms per molecule (run 13); and dearomatized Webster Crude having a boiling range of 204-260" C., an average of 13 carbon atoms per molecule, and 'n =l;4546 (run C). Data obtained are as follows:

Run A Run B Run 0 Reaction temperature C. 100 100 100 Charge: benzene, g 201 200 200 saturate, g 101 100 125 hydrogen fluoride, g. 131 112 126 isobutylene, g 60 71 73..5 Alkylated benzene product, g 56 119' 63 Yield, mole percent (Based on saturates consumed) 78 100 64 Saturates recovered, g. 52. 5 57 56. 5 Benzene recovered, g 143 141 124 --To illustrate recovery of the alkylated benzene products of the process ofthe invention, in run B of the above table,

Run B Run 0 benzene".-. 48. 5 42. 7 saturates 13. 6 21. 5 t-butylbenzen 4. 6 14. 6 intermediate boiling (not identified). 10.6 1. 8 alkylated product 22.7 19. 4

.The alkylated product of the table consisted of the products. of alkylation between benzene and the saturates having at least one tertiary hydrogen atom of the petroleum fractions employed. After separation by distillation, as above described, a small amount of high boiling material, about 10 g. in run B and about 20 g.- in 'run C, remained unidentified.

Example 4 Two experiments were made at different temperatures using dearomatized second-pass catalytic gas-oil as the saturate material. This saturate material contained about 70.8% of isoparaffins and about 26.2% of isoparafiins including a naphthene ring, the remainder being aromatics and a small amount of olefins; the average molecular weight was 222 (16 carbon atoms per molecule), and n =1.4505.

The procedure was to introduce the saturate, benzene and hydrogen fluoride into a contactor provided with a stirrer, and then introduce isobutylene into the agitated mixture at room temperature. The mixture was then heated to the indicated temperature for the specified time, with continued stirring, after which it was transferred to a copper vessel cooled to -78 C., and the components thereof separated by decantation and distillation. Operational variables and results are summarized below:

Run A Run 13 Reaction temperature C... 100

, High boiling residue 12 5 -Wt. percent of total charge recovered 81. 8 86. 3

Including isobutane, t-butylbenzene, and dt-t-butylb enzenc.

Example 5 Example 4 was repeated at C. except that va larger quantity of benzene was employed. Quantities of reactants were: 202 g. benzene, 101 g. saturates, 51.2 "g. isobutylene, and 123.5 g. hydrogen fluoride.

There were recovered 30.5 g. of alkylated benzene (yield=56 mol percent based on saturates consumed), and 60.5 g. of saturates, together with the by-products mentioned in Example 4, including 6 g. of high boiling residue. Weight percent of the total charge recovered was 92.

Example 6 4 was followed. Operational variables and results were as follows:

RunA RunB RunC Reaction temperature 0.. 100 100 25 Charge:

Alkylated aromatic product, g Yield, mole percent (based on saturates consumed) 94 59 8 saturates recovered, g 98 113. 4 141 Aromatics recovered:

toluene, g 117 mixed xylenes. 70. 5 m-xylene, g 12. 9

In run C, which was performed at 25 C., there were also obtained 120.5 g. of tertiary butyl-m-xylene, which shows the substantial alkylation of the aromatic with the tertiary olefin at temperatures below about 50 C., as above described. By way of comparison, in run A, only 23 g. of tertiary butyltoluene were obtained.

8 mole percent yield, based on saturates reacted, being 46.5%. The product had a boiling range of 291374 C. and an average molecular weight of 275 (theoretical molecular weight=287).

Example 9 Example 7 was substantially duplicated using, as the saturate material, Webster dearomatized two-pass catalytic fractions having boiling ranges of 149204 C., 204 260 C., and 260-316 C., their average molecular Example 10 Example 7 was substantially duplicated, using Webster saturate fractions as therein described, and the 204- 260 C. fraction described in Example 9, to alkylate Example 7 alpha-methyl naphthalene. Data obtained are as fol- A Webster straight run dearomatized saturate was seplows:

saturate traction C.) 149-260 204-260 260-316 1 204-260 Product obtained, g 91. 5 89. 5 81. 5 62 Yield, mole percent (based on saturates reacted) 69. 2 54. 0 65. 2 53. 8 Average molecular weight of product. 288 268 268 316 313 Theoretical molecular weight oi pro uct 286 286 325 366 336 Boiling range of product 166-243 160-191 160-188 157-263 188-248 1 Alkylation at 60 0.; all others were at C. 1 Instead 01 13, Webster traction, a fraction of second-pass catalytic gas-oil was used.

arated into fractions by distillation. The various fractions were used to alkylate benzene, g. of the saturate and 150-151 g. of benzene being employed in each instance.

The technique employed was substantially as described in Example 4: the benzene, saturate and hydrogen fluoride were introduced into a contactor equipped with a stirrer. The mixture was agitated at room temperature while the isobutylene was introduced over a period of about two minutes. There was appreciable warming of the reaction mixture. The stirred mixture was then heated to 100 C. for 90 minutes. The maximum pressure developed was p. s. i.

The contactor was cooled in an ice bath to 0 C. and

Example 11 The Webster 260-316 C. saturate fraction described 40 in Example 7 was employed to alkylate toluene, the quan- Example 12 To 150 g. of a fraction of Webster crude boiling be- .0 the hydrogen fluoride removed. The organic layer was tween 204 and 260 C., and contaming 1ts natural arowashed with water and distllled. matics and saturates, were added 150 g. of benzene and Saturate Yield Boning Range Molecular Saturates g Product (wt. pergf figzigg $352k": cular Wt.

(a 0') Weight (Vghgera (g.) cent) Sammtes Y otProduct a; a. 11% @2 a a: I as m a; at a a 22 2 43s 1 9713 ms 1e 12 23:3 "'a'sf'e IIIIIIIIIIIIIIIIIII I Determined by boiling point-density correlation method described in 1nd. En Chem. 38 442 1946 3 Calculated from known molecular weights of the benzene and saturate.

l Allrylation at 25 C. instead of 100 0.

Example 8 Example 7 was substantially duplicated using, as the saturate, an East Texas straight run dearomatized fraction having a boiling range of 204-260 C., an average molecular weight of 211, n =1.4377,.and containing 99.7 vol. percent of saturates.

There were obtained 50 g. of alkylated product, the

134.5 g. of hydrogen fluoride. 72 g. of isobutylene was 79 introduced into the mixture over a period of 8 minutes,

5 saturates reacted, of 54%.- The product had a boiling range of 281.6-356" C., an average molecular'weight of 234, and n =1.51.60.

Example 13 and ultimate, were so low that the process must be considered practically inoperative.

Other embodiments are obviously included within the I scope of the present invention, such as the addition of hydrogen fluoride to a mixture of aromatic, saturate and tertiary olefin, instead of addition of the tertiary olefin, as hereinbefore described, though the latter is preferred. It is not permissible, however, to premix the hydrogen fluoride and tertiary olefin in the absence of the aromatics and saturate, since polymerization of the olefin will result. It is also permissible to employ a small amount of boron trifluoride as a promoter for the reaction, in which case, lower temperatures than otherwise would be employed are preferred. However, the use of such prometers is generally unnecessary, and is not preferred, especially in view of their high cost and the fact that they cause undesired reactions, such as polymerization of the tertiary olefin, cracking, and the like.

The foregoing examples illustrate preferred embodiments of the present invention, including the use of aromatics from petroleum fractions, and the use of an entire fraction including aromatics, isoparaflins, and naphthenes in the process. The process of the present invention may be carried out by batch, intermittent, or continuous processes.

The lower molecular weight alkyl-aromatic products prepared in accordance with the present invention may be employed in fuel compositions, as lubricating and cut ting oil additives, and in the preparation of detergents.

This application is a continuation-in-part of application Serial No. 96,754, filed June 2, 1949, now abandoned.

The invention claimed is:

1. An alkylation process which comprises bringing together in the liquid phase at a temperature of from 50 C. to 200 C., hydrogen fluoride and a tertiary monoolefin in the presence of an alkylatable aromatic hydrocarbon and a saturate hydrocarbon having at least 5 carbon atoms and 1 tertiary hydrogen atom, wherein the mole ratio of said saturate to said aromatic hydrocarbon is from 5:1 to 1:6 and the mole ratio of said tertiary mono-olefin to said aromatic hydrocarbon plus said isoparaflin hydrocarbon is from 1:10 to 1:1, whereby said isoparaflin alkylates said aromatic hydrocarbon to form an alkyl aromatic having an alkyl substitutent containing the same number of carbon atoms as said isoparaffin hydrocarbon, and separating said alkyl substituted aromatic hydrocarbon from the reaction mixture.

2. The process according to claim 1 wherein the tertiary olefin is isobutylene.

3. An alkylation process which comprises bringing together in the liquid phase at a temperature of from 50 C. to 200 0., hydrogen fluoride and a tertiary monoolefin in the presence of benzene and an isoparaflin hydrocarbon having at least 1 tertiary hydrogen atom, wherein the mole ratio of said isoparaflin to benzene is from 5:1 to 1:6 and the mole ratio of said tertiary monoolefin to said isoparaflin plus benzene is from 1:10 to 1:1, whereby said isoparaffin alkylates said benzene to form an alkyl benzene having an alkyl substituent con taining the same number of carbon atoms as said isoparaflin hydrocarbon, and separating from the reaction mixture said alkyl substituted benzene.

4. The process according to claim 3 wherein the isoparaflin hydrocarbon is a saturate hydrocarbon fraction.

5 The process according to claim 4 wherein the tertiary olefin is isobutylene.

6. An alkylation process which comprises bringing together, in the liquid phase at a temperature of from 50 C. to 200 .C., hydrogen fluoride and isobutylene in the presence of benzene and a saturate hydrocarbon fraction composed substantially of a mixture of branched chain parafiins having an average of at least 1 tertiary hydrogen atom per molecule boiling between 149 C. and 482 C., wherein the mole ratio of said saturate hydrocarbon fraction to said benzene is from 5 :1 to 1:6, and wherein the mole ratio of isobutylene to benzene plus said saturate hydrocarbon fraction is from 1:10 to 1:1, whereby said saturate alkylates said benzene to form an alkyl substituted benzene wherein the alkyl substituent contains the same number of carbon atoms as said saturate, and separating said alkyl substituted benzene from the reaction mixture.

7. The process according to claim 6 wherein the mole ratio of hydrogen fluoride to benzene plus saturate hydrocarbon fraction is from 8:1 to 1:1.

8. An alkylation process which comprises bringing together, in the liquid phase at a temperature of from 50 C. to 200 C., hydrogen fluoride and a tertiary monoolefin in the presence of toluene and an isoparaflin hydrocarbon having at least 1 tertiary hydrogen atom, wherein the mole ratio of said isoparaflin to said toluene is from 5:1 to 1:6 and the mole ratio of said mono-olefin to toluene plus said isoparaffin is from 1:10 to 1:1, whereby said isoparafiin alkylates said toluene to form an alkyl aromatic having an alkyl substituent containing the same number of carbon atoms as said isoparafiin hydrocarbon, and separating said alkyl substituted toluene from the reaction mixture 9. The process according to claim 8 wherein the tertiary olefin is isobutylene and the isoparaflin is a saturate hydrocarbon fraction.

10. The process according to claim 9 wherein the mole ratio of hydrogen fluoride to toluene plus saturate is from 8:1 to 1:1.

11. An alkylation process which comprises bringing together, in the liquid phase at a temperature of from 50 C. to 200 C., hydrogen fluoride and a tertiary monoolefin in the presence of a petroleum hydrocarbon fraction containing alkylatable aromatics and isoparaffins wherein said isoparatfins have more than 5 carbon atoms per molecule and at least 1 tertiary hydrogen atom per molecule, and wherein the mole ratio of said isoparaifins to said aromatics is from 5:1 to 1:6 and the mole ratio of said tertiary mono-olefin to said isoparaflins plus said aromatics is from 1:10 to 1:1, whereby said isoparaflins alkylate said alkylatable aromatics to form alkyl substituted aromatics wherein an alkyl substitutent thereof contains the same number of carbon atoms as said isoparaflin, and separating said alkyl substituted aromatics from the reaction mixture.

12. The process according to claim 11 wherein the tertiary olefin is isobutylene.

13. Process for the alkylation of aromatics with isoparaflins which comprises bringing together in the liquid phase at a temperature of from 50 C. to 200 C., hydrogen fluoride and a tertiary mono-olefin in the presence of an aromatic hydrocarbon and an isoparafjn hydrocarbon whereby a catalytic condition is established eflFective to cause said isoparafiin to alkylate said aromatic, said tertiary mono-olefin being converted to the corresponding paraflin, the mole ratio of isoparaflin to aromatic being from 1:5 to 6:1, the mole ratio of tertiary mono-olefin to aromatic plus isoparaflin being from 1:10 to 1:1, and the mole ratio of hydrogen fluoride to aromatic plus isoparafiin being from 1:1 to 8:1, mixing said reaction mixture for from A to 2 hours, and recovering an alkylated aromatic product wherein an alkyl radi- 11 12 cal'contains the same number of carbon atoms as said 2,653,980 Condon Sept. 29, 1953 mpmflin' I OTHER REFERENCES References Cited in the file of this patent Condom et a1.,: Jour. Am. Chem. Soc., vol. 70, pages UNITED STATES PATENTS 5 25394542 (July 1948* 2,626,966 Kennedy et a] Jan. 27, 1953 

1. AN ALKYLATION PROCESS WHICH COMPRISES BRINGING TOGETHER IN THE LIQUID PHASE AT A TEMPERATURE OF FROM 50* C. TO 200* C., HYDROGEN FLUORIDE AND A TERITARY MONOOLEFIN IN THE PRESENCE OF AN ALKYLATABLE AROMATIC HYDROCARBON AND A SATURATED HYDROCARBON HAVING AT LEAST 5 CARBON ATOMS AND 1 TERTIARY HYDROGEN ATOMS, WHEREIN THE MOLE RATIO OF SAID SATURATE TO SAID AROMATIC HYDROCARBON IS FROM 5:1 TO 1:6 AND THE MOLE RATIO OF SAID TERTIARY MONO-OLEFIN TO SAID AROMATIC HYDROCARBON PLUS SAID ISOPARAFFIN HYDROCARBON IS FROM 1:10 TO 1:1, WHEREBY SAID ISOPARAFFIN ALKYLATES SAID AROMATIC HYDROCARBON TO FORM AN ALKYL AROMATIC HAVING AN ALKYL SUBSTITUTENT CONTAINING THE SAME NUMBER OF CARBON ATOMS AS SAID ISOPARAFFIN HYDROCARBON, AND SEPARATING SAID ALKYL SUBSTITUTED AROMATIC HYDROCARBON FROM THE REACTION MIXTURE. 